Organotitanium compounds and method for preparing the same



F 2,886,579 Patented May 12, 1959 ORGANOTITANIUM QOMPOUNDS AND METHOD FOR PREPARING THE SAME Daniel F. Herman, Orange, N.J., assignor to National :Ifead Company, New York, N.Y., a corporation of New ersey No Drawing. Original application July 12, 1956, Serial No. 597,344. Divided and this application December 5, 1957, Serial No. 700,752

9 Claims. ((3. 26ll-429.5)

This invention relates to novel organotitanium compounds. More particularly, it relates to organotitanium compounds involving a stable carbon-titanium bond. Still more specifically, this invention relates to aryltitanium alkylates and to methods for preparing the same.

This application is a divisional application of my application Serial No. 597,344, filed July 12, 1956. Application Serial No. 597,344 is a continuation-in-part of application Serial No. 339,456, filed February 27, 1953.

Numerous attempts have been made in the past to 'produce compounds involving direct carbon-titanium bonds, however, all attempts have been unsuccessful since they tried to replace all of the substituents on the titanium with alkyl or aryl groups.

It is an object of this invention, therefore, to provide novel organotitanium compounds. A further object is to provide novel organotitanium compounds which contain carbon-titanium bonds. A particularly desirable object is to produce such carbon-titanium bonded compounds which are sufliciently stable to permit the preparation of such compounds in quantity for storage prior to use. It is also an object of this invention to provide methods for the manufacture of such compounds. Other objects and advantages of the present invention will become apparent from the following more complete description and claims.

In its broadest aspects this invention contemplates an aryltitanium trialkylate, said aryltitanium trialkylate being an ester of tetravalent titanium wherein one of the four valencies of said tetravalent titanium is satisfied by an aryl group through a direct carbon-titanium bond, and the remaining three valencies of said titanium are satisfied by alkoxy groups through oxygen-titanium bonds. The aryl group in said aryltitanium trialkylate may be phenyl, substituted phenyl, naphthyl or substituted naphthyl groups. The substituents in said substituted phenyl or naphthyl groups are lower alkoxy, lower alkyl and phenyl.

This invention further contemplates a particular complex formation which is the equimolecular addition compound of phenyltitanium triisopropylate, lithium isopropylate, lithium bromide and ethyl ether, having the formula:

This invention also contemplates the method of producing aryltitanium trialkylate which comprises reacting a tetraalkyl orthotitanate or an alkoxytitanium halide with an aryl Grignard reagent or metal aryl, said tetraalkyl orthotitanate or alkoxytitanium halide being present in amount to provide at least one mole of tetraalkyl orthotitanate or alkoxytitanium halide for each equivalent of said Grignard reagent or metal aryl, i.e. no 'excess of the aryl Grignard reagent or metal aryl should be employed.

Previous attempts to prepare compounds containing carbontitanium bonds have apparently always proceeded along the lines of selecting amounts of reagents suflicient for the substitution of four alkyl or aryl groups for the.

chloride or alkoxy groups in the titaniferous starting material (tetraalkyl orthotitanates or alkoxytitanium chlorides, for example). However, compounds of tetravalent titanium having more than two TiC bonds are, for all practical purposes, non-existent.

It has now been discovered that it is possible to prepare compounds containing only 1 or 2 TiC bonds for each titanium atom and that these compounds are relatively stable, and in some cases may be produced in bulk and stored for reasonable lengths of time (i.e. several days and in some cases several months or even years) before use.

It has further been found that these compounds may be produced in good yield and without undue difiiculty by avoiding the addition of proportions in excess of 2 moles of arylating agent to 1 mole of titanium compound. Thus the quantities of reactants employed should be substantially not in excess of those which will theoretically produce one or two TiC bonds for each titanium atom, i.e. one or two equivalents of metal aryl or aryl Grignard reagent for each atom of titanium in the titaniferous starting material. Moreover, it has been found that the stability of the products is enhanced if the amount of the metal aryl or aryl Grignard reagent is somewhat less than that required to react with all of those having from 1 to 6 carbon atoms in the hydrocarbon chain. Among those which are the most readily available are methyl, ethyl, isopropyl, butyl and cyclohexyl.

The aryl groups just described may be employed in the form of aryl Grignard reagents or metal aryls.

Among the aryl Grignard reagents which are most desirable are those of magnesium, aluminum and zinc.

Metal aryls which are the most useful are those of Li,

Mg, Al, Cd, Zn, Ca, Na and K. Typical compounds of such aryl Grignard reagents and metal aryls include, for

example, phenylma gnesium bromide, tolylithium, ptolylithium, phenylaluminum chlorides, diphenylzinc, diphenylcadmium, diphenylmagnesium, sodium naphthyl-l, phenylcalcium iodide, potassium naphthyl-2 and the like.

'The alkoxy groups of the titaniferous starting material according to the present invention may be substituted or unsubstituted and saturated or unsaturated groups containing up to about 16 carbon atoms. It is preferred,

however, to use alkoxy groups having less than six carbon atoms, because such groups are more reactive, and

give products, in general, which are more readily isolated.

The preferred method of preparation of the aryltitanium trialkylate according to this invention is simply to add the aryl Grignard reagent or metal aryl to the tetraalkyl orthotitanate or alkoxytitanium halide in stoichiometric proportions and in the presence of a solvent such as ether, to produce a monoaryltitanium trialkylate, the process being carried out in inertatmosphere at or slightly below room temperature. Theresulting product is a solid suspension or 'a solution of aryltitanium trialkylate or complexes thereof.

The products prepared from metal aryls, e.g. lithium aryl, tend to form complexes with the by-products and other substances present in the system (e.g. the solvent). In some cases (for example that in which phenyltitanium triisopropylate is prepared from phenyllithium and titanium tetraisopropylate in a diethyl ether medium) the complex formed is suificiently insoluble to precipitate out, and can then be separated by decantation, filtration or the, like.

In preparing the phenyltitanium triisopropylate complex from phenyllithium and titanium tetraisopropylate, the phenyllithium may be prepared in the following manner.

Lithium metal shot is placed in anhydrous ether and bromobenzene is added dropwise. The reaction may be represented by the following equation:

since the LiBr formed is soluble in ether, the LiBr remains in solution together with the phenyllithium.

The phenyllithium containing ether solution (which also contains the LiBr), is added slowly to a tetraalkyl orthotitanate, as for example, titanium tetraisopropylate. A white crystalline insoluble solid complex is obtained. The reaction and the analytical results substantiated that the complex formed has the following composition:

The reaction is as follows:

In other cases, the complex may be soluble, in which case it is not easily separated as such, usually breaking down to give the free aryltitanium trialkylate. When the magnesium Grignards are used, for example, the formation of a complex apparently does not take place, or if it does, the complexes formed are soluble and too unstable to be isolated as such. However, when complexes are formed, they are frequently more stable than the aryltitanium trialkylate itself, and thus offer a convenient form in which to handle, purify and store these compounds.

When it is desired to separate the aryltitanium trialkylate from a complex such as described above and having the formula:

it has been found that this may be accomplished by adding to each mole of the complex, one equivalent of an organo-soluble metal halide capable of reacting metathetically with lithium alcoholates to form the corresponding metal alcoholates and lithium halides. Many examples of such compounds include metal halides which are Lewis acids, among which are halides of silicon, titanium, tin, aluminum, boron and zirconium and the like.

It is preferred to use the halides of titanium since they have the additional advantages that the titanium tetra-alcoholate produced does not complicate the system by the introduction of foreign substances. Whatever metal halide is employed, it is preferred, for the sake of convenience, to add the same as a solution in a suitable solvent such as ethyl ether or petroleum ether. The other product of the metathesis, that is, the lithium. halide, forms an inert precipitate and may be separated by filtration or any other convenient means. The aryltitaniurn trialkylate may then be recovered by ordinary methods, for example, stripping off the solvent by vacuum evaporation. Suitable precautions should, of course, be observed to avoid atmospheric oxidation or moisture contamination. In some cases, when the titanium tetrahalide is dissolved in a solvent which also is capable of dissolving appreciable amounts of lithium halide, such as ethyl ether for example, it isdesirable to modify the solvent system by evaporating a portion of the original solvent and replacing it with one which does not dissolve any appreciable quantity of lithium halide. Petroleum ether is such a solvent.

In order to effect the separation of the aryltitanium trialkylate from the complex by reacting the complex with a metal halide, the metal halide should be added slowly to the crystallized complex in the presence of ether and the complex slowly dissolved as the reaction proceeded. The solution obtained is then cooled to form the aryltitanium trialkylate. The following equation illustrates the type of reaction which occurs:

In order to more fully illustrate the nature and preparation of the novel organotitanium compounds of this invention. the following examples are presented.

Example 1 841.4 parts of tetraisopropyl titanate were dissolved in 1500 parts of anhydrous diethyl ether and the resulting solution was admixed in a water-jacketed glass-lined vessel with 248.8 parts of phenyllithium as a 1 N solution in diethyl ether. The mixing operation took place over a period of 2 /2 hours during which time the jacket was supplied with cooling water to maintain the temperature of the mixture at around 18 C. The entire operation was carried out under an atmosphere of dry nitrogen. Throughout the mixing period and for an additional short time thereafter, the mixture in the vessel was agitated by means of a glass covered sweep agitator. As the phenyllithium solution was added to the isopropyl titanate, the mixture gradually darkened to a clear amber. When approximately of the phenyllithium had been added, a white crystalline solid began to precipitate. A portion of this solid was analyzed and was found to be an addition compound of phenyltitanium triisopropylate, lithium isopropylate, lithium bromide and diethyl ether, corresponding to the formula:

This addition compound was separated by centrifugation from the liquid portion of the m'mture which was essentially diethyl ether containing a small amount of dissolved phenyltitanium triisopropylate complex. 530 parts of the separated addition compound were then dispersed in 500 parts of petroleum ether (3060 C. boiling point) and treated over a period of 1 /2 hours with 52 parts (about 10% excess) of titanium tetrachloride dissolved in 500 parts of diethyl ether. Agitation, cooling and inert atmosphere were again maintained as above described and the agitation was again continued for a short time after the reaction appeared to be complete. As the titanium tetrachloride solution was added, the major portion of the solid material disappeared, to be replaced by a much smaller volume of fine crystals which, upon subsequent analysis, proved tobe lithium chloride and lithium bromide. These crystals were separated by centrifugation from the liquid portion. of the mixture and the liquid portion, consisting essentially of phenyltitanium triisopropylate dissolved in the mixture of solvents, was subjected to vacuum distillation at room temperature to strip off a portion of the solvents. Pressure employed was -200 millimeters. When about half. of the solvents had been stripped oif, the product, phenyltitanium triisopropylate, crystallized in goodv yield, and was separated by decantation. The entire procedure, from the original admixture of phenyllithium solution with tetraisopropyl titanate to the final decantation and separation of phenyltitanium triisopropylate, was carried out in the presence of a nitrogen atmosphere.

A. portion of the phenyltitanium triisopropylatelithiunr isopropylate-lithium bromide-ether complex intermediate was stored for two years at room temperature and then.

was treated with titanium tetrachloride solution to produce phenyltitanium triisopropylate in the manner above described. The purity and reactivity of the complex and the yield in which phenyltitanium triisopropylate was recovered were substantially unaffected by the storage.

Phenyltitanium triisopropylate is a white crystalline material melting at 8890 C. to give a clear yellow liquid, which decomposes on heating to 120 C. It, readily oxidizes in air and decomposes upon warming to trivalent titanium compounds and free phenyl radicals. It may, however, be stored indefinitely at C.

In order to illustrate the use of phenyltitanium triisopropylate as a polymerization catalyst, a portion of phenyltitanium triisopropylate prepared as above described was used in the polymerization of styrene according to the following procedure. One part of phenyltitanium triisopropylate was dissolved in a mixture of 200 parts of benzene and 200 parts of styrene and the mixture was heated for five hours at 80 C. For purposes of comparison, a similar procedure was employed using one part of benzoyl peroxide dissolved in a mixture of 200 parts of benzene and 200 parts of styrene. The yields of polymers produced were approximately identical in both cases.

Example 2 176.5 parts of phenyllithium dissolved in 1000 parts of diethyl ether were added slowly to 596.9 parts of isopropyl titanate dissolved in 1450 parts of diethyl ether. The addition took place over a period of 1% hours and the reaction was essentially complete at the end of that time. The entire operation was carried out at approximately room temperature and under an atmosphere of dry nitrogen. To this mixture was added 120 parts of titanium tetrachloride dissolved in 2000 parts of ether. Lithium chloride precipitated and was separated from the mixture by decantation. To the remaining liquid portion of the mixture were added 382.6 parts of benzophenone dissolved in 500 parts of ether. The mixture was stirred and then allowed to stand overnight, and subsequently refluxed 7 hours. The so-produced addition compound was subsequently hydrolyzed by adding to it 4000 parts of 5% H 80 The reaction mixture separated into two layers, a water layer containing sulfuric acid, titanium sulfate and isopropyl alcohol in solution, and an ether layer containing the product, triphenylcarbinol. The two layers were separated by decantation. The ether layer was washed with water, stripped of part of its ether by distillation under reduced pressure on the steam bath and finally steam-distilled to separate the triphenylcarbinol from impurities. The steam distillate was then extracted with ether and the ether extract distilled at four millimeters pressure to remove residual unreacted benzophenone. The residue, which crystallized on cooling, was recrystallized from carbon tetrachloride and had a melting point of 162- 163 C., and was found to be essentially pure triphenylcarbinol.

Example 3 Approximately 775 parts (theoretical) of a-naphthylmagnesium bromide were prepared from 690 parts of a-bromonaphthalene and 85 parts of magnesium in 3000 parts of ether according to the usual procedures for the preparation of Grignard reagents. The Grignard reagent crystallized and a thick yellow slurry resulted. This slurry was added gradually over a period of one hour through a wide rubber tube to a glass vessel equipped with a stirrer and containing 1140 parts of tetrabutyl titanate dissolved in 3000 parts of ether. The entire procedure was carried out in an inert atmosphere of circulating dry nitrogen. The insoluble Grignard reagent dissolved immediately upon introduction indicating a 6', very rapid reaction. When theladdition'was complete the reaction mixture was a clear brownish-orange solution containing a-naphthyltitanium tributylate. This solution was used without further purification for the polymerization of styrene according to the procedure described in Example 1, using 5 parts of the solution and 40 parts of styrene dissolved in 35 parts of benzene. The results were similar to those produced both by phenyltitanium triisopropylate and by benzoyl peroxide in Example 1.

Example4 A Grignard reagent was prepared by adding 684 parts of p-bromotoluene to 97 parts of magnesium in 2000 parts ethyl ether. This Grignard reagent was added in small portions over a period of 55 minutes to 1360 parts of butyl titanate dissolved in xylene and cooled to 15 C. The insoluble Grignard reagent again dissolved immediately upon introduction, to produce a clear amber solution containing p-tolyltitanium tributylate.

Example 5 The procedure of Example 3 was repeated, substituting for the a-bromonaphthalene an equivalent quantity of p-anisyl bromide. The product was p-anisyltitanium tributylate.

The organotitanium compounds of this invention are the first successfully prepared stable organic compounds containing a direct carbon-titanium bond. They are useful as reactive intermediates in the synthesis of more complex organic and organotitanium compounds, as catalysts for the polymerization of styrene and in various other ways which the unique chemical structure of these compounds will suggest to those skilled in the art.

While this invention has been described and illustrated by the examples shown, it is not intended to be strictly limited thereto, and other modifications and variations may be employed within the scope of the following claims.

I claim:

1. As a new composition of matter, an aryltitanium trialkylate, said aryltitanium trialkylate being an ester of tetravalent titanium wherein one of the four valencies of said tetravalent titanium is satisfied by an aryl group through a direct carbon-titanium bond, and the remaining three valencies of said titanium are satisfied by alkoxy groups through oxygen-titanium bonds, said aryl group being selected from the group consisting of phenyl, substituted phenyl, naphthyl and substituted naphthyl, the substituent in said substituted phenyl and substituted naphthyl are selected from the group consisting of lower alkoxy, lower alkyl and phenyl.

2. The complex addition compound of phenyltitanium triisopropylate, lithium isopropylate, lithium bromide and diethyl ether having the formula:

C H Ti(OC H -Li(OC H -LiBr- (C H O 3. As a new composition of matter, a phenyltitanium trialkylate having the formula:

C H Ti(OR) wherein R is an alkyl group containing from 1 to 16 carbon atoms.

4. As a new composition of matter, an a-naphthyltitanium trialkylate having the formula:

1o 'I )a wherein R is an alkyl group containing from 1 to 16 carbon atoms.

5. As a new composition of matter, a p-anisyltitanium trialkylate having the formula:

wherein R is an alkyl group containing from 1 to 16 carbon atoms.

'6. Method for preparing an organic compound of titanium which comprises reacting a titanium alcoholate with an organornetallic arylating agent selected from the group consisting of metal aryls and aryl Grignard reagents, said arylating agent being present in an amount not exceeding one equivalent for each titanium atom in said titanium alcoholate, the aryl group in said arylating agent being selected from the group consisting of phenyl, substituted phenyl, naphthyl and substituted naphthyl, the substituents in said substituted phenyl and said substituted naphthyl being selected from the group consisting of lower alkoxy, lower alkyl and phenyl.

7. Method according to claim 6 in which the organometallic arylating agent contains a metal selected from the group consisting of magnesium, aluminum, cadminum, zinc, calcium, sodium and potassium.

8. Method of preparing an organic compound of titanium alcoholate with a lithium aryl in amount not exceeding one equivalent for each titanium atom in said titanium alcoholate to form a complex addition compound comprising an aryltitanium trialkylate and a lithium alcoholate, and breaking down said complex addition compound by adding thereto a metal halide capable of reacting metathetically with said lithium alcoholate.

9. Method of preparing an organic compound of titanium which comprises reacting a titanium alcoholate with a lithium aryl in amount not exceeding one equivalent for each titanium atom in said titanium alcoholate to form a complex addition compound comprising an aryltitanium trialkylate and a lithium alcoholate, and breaking down said complex addition compound by adding thereto a metal halide selected from the group consisting of a halide of silicon, tin, aluminum, boron, titanium and Zirconium.

References Cited in the file of this patent Gilman et al.:

J. A. C. S., 76, pages 3615-3617 (1954). 

1. AS A NEW COMPOSITION OF MATTER, AN ARYLTITANIUM TRIALKYLATE, SAID ARYLTITANIUM TRIALKYLATE BEING AN ESTER OF TETRAVALENT TITANIUM WHEREIN ONE OF THE FOUR VALENCIES OF SAID TETRAVALENT TITANIUM IS SATISFIED BY AN ARYL GROUP THROUGH A DIRECT CARBON-TITANIUM BOND, AND THE REMAINING THREE VALENCIES OF SAID TITANIUM ARE SATISFIED BY ALKOXY GROUPS THROUGH OXYGEN-TITANIUM BONDS, SAID ARYL GROUP BEING SELECTED FROM THE GROUP CONSISTING OF PHENYL, SUBSTITUTED PHENYL, NAPHTHYL AND SUBSTITUTED NAPHTHYL, THE SUBSTITUENT IN SAID SUBSTITUTED PHENYL AND SUBSTITUTED NAPHTHYL ARE SELECTED FROM THE GROUP CONSISTING OF LOWER ALKOXY, LOWER ALKYL AND PHENYL.
 2. THE COMPLEX ADDITION COMPOUND OF PHENYLTITANIUM TRIISOPROPYLATE, LITHIUM ISOPROPYLATE, LITHIUM BROMIDE AND DIETHYL ETHER HAVING THE FORMULA: 